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In this chapter we will introduce the concepts of work and
energy, which will lead to the 1st Law of Thermodynamics.
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Configuration work: We consider some reversible process
đ W= (intensive variable ) (change in extensive variable)
Let y=intensive variable X= extensive variable
dW y dX
i
i i
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Consider a system and its surroundings.
surroundings
system
When the system as a whole
does work on the surroundings or the
surroundings do work on the system as a whole, we
call this external work.
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Convention:
A
F P
PISTON (adiabatic)
The gas expands by exerting a pressure
infinitesimally greater than the pressure on the
gas exerted by the force acting on the piston.
F=PA (good approx.)
The work done by the gas is
đW = Fdx = PAdx
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đW because this is an inexact differential.
W is not a function of the system variables
W W(P,V,T).
We cannot write dW WT P dT WP T dP
Volume increases and Adx = dV
đ W = PdV
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PV Diagrams (Indicator Diagrams)
Wi f Pd V
Vf
is positive
P i Vi
f
Work done by system.
V
Wf i Pd V
Vi
i is negative
Vf
P Work done on system.
f
V
A cycle
i W PdV (not zero!)
P f Net work is positive.
V Net work done by system 9
Work is not a state function.
Work is an activity or process that results in a
change of the state of a system.
In going from an initial thermodynamic state to a
final state through intermediate states, the work
done will depend on the path taken.
i Vf
W
I
P Pd V
Vi
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Calculation of work for quasi-static processes
Isothermal expansion of an ideal gas:
i Vf
P W
Vi
Pd V
dV
f Vf
P V nRT W nRT
V
Vi
V
Vf
T constant so W nRT ln Vi
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Isothermal increase of the pressure on a solid
We defined:
1
V
V
T P
Volume expansivity
V1 VP T Isothermal compressibility
V T, P dV
dT dP
V
T P
V
P T
đ W P V dP
For a solid Vconstant and over a limited range constant.
W V W V P P
Pf
1 2 2
PdP 2 f j
Pi
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Dissipative work
Dissipative work is work done in an irreversible process. It
is always done on a system. (We will discuss irreversible
processes later in the course.) Dissipative effects include friction,
viscosity, inelasticity, electrical resistance and magnetic hysteresis.
If there are no dissipative effects, all the work done by the
system in one direction can be returned to the system during the
reverse process.
vacuum
diaphragm gas
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Adiabatic work.
Consider a system going from some initial state i to a final
state f. Many different processes are possible and the work done
will depend on the path taken.
Now we limit ourselves to adiabatic paths. (System surrounded
by an adiabatic boundary and so the temperature of the system is
independent of that of the surroundings. No energy transfer.)
Consider the processes shown on the PV diagram below:
adiabatic i
expansion free expansions
a adiabatic expansion
P b f
work
V
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First, we have a free expansion (no work) from i to a, then an adiabatic
expansion from a to f. The work done by the system is the area under the af
curve.
Notice that the free expansions are denoted by dotted lines because they do
not proceed quasi-statically through a series of equilibrium states. The area
under these dotted lines is not the work done. (The work done is, of course,
zero.)
It is an experimental fact that the work done during these two different
processes is the same.
The total work is the same in all adiabatic processes between any two
equilibrium states having the same kinetic and potential energy!!! This is
called the restricted statement of the first law of thermodynamics. 16
Because of this independence of path (for these adiabatic processes)
there exists a function of the thermodynamic coordinates of the
system such that
Wi f ( adiabatic) (U f Ui )
V
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Heat is a process, not a quantity of anything. It is not correct to say
“heat in a body”. After a process is completed, there is no further
use for Q.
The differential form of the first law is :
dU=đQ-đW
We have described how to calculate a reversible đW in a hydrostatic
(i.e. P,V,T) system: đWrev=PdV and so dU= đQ-PdV.
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EXAMPLE: Chapter 3
Compute the work done against atmospheric pressure when 10kg
of water is converted to steam occupying 16 . 7 m3
kg m 10 kg
For water 103
m V V V 10 2 m3
m3 3 kg
10
m3
Vf
W PdV P(V
Vi
f Vi )
W 1 . 69 10 6 J
The system, initially water, does work in pushing aside the atmosphere.
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EXAMPLE: Chapter 3
Steam at a constant pressure of 30atm is admitted to the cylinder of a
steam engine. The length of the stroke is 0.5m and the radius of
the cylinder is 0.2m. How much work is done by the steam per stroke?
W PdV V Ax dV Adx
xf
W PA dx PA( x f xi )
xi
W 1 . 90 10 5 J
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EXAMPLE: Chapter 3
A volume of 10 m3 contains 8 kg of oxygen at 300K. Find the
work necessary to decrease the volume to 5 m3
(a) At constant pressure
(b) At a constant temperature
(c) What is the temperature at the end of process (a)?
(d) What is the pressure at the end of process (b)?
(e) Show both processes on an indicator (PV) diagram.
We assume an ideal gas law equation of state.
8 kg
O2 2 (16 )amu 32 amu n n 0 . 25 kmole
kg
32
kmole
(a) Constant P
J
0 . 25 kmole(8 . 314 10 3 )300 K
Pi
nRTi
kmole K Pi 6 . 24 10 4 Pa
Vi 10 m3
24
Vf
W
4 3 3
PdV Pi (V f Vi ) 6 . 24 10 Pa(5 m 10 m )
Vi
W 3 .12 10 5 J
Vf
Vf
nRT
(b) Constant T P W PdV nRT ln
V Vi Vi
J 1
W 0 . 25 kmole(8 . 314 10 3
)( 300 K ) ln
kmole K 2
W 4 .32 10 5 J
Ti T f Vf
(c) For constant P V V T f Ti 300 K 1 T f 150 K
i f Vi 2
Vi
(d) Constant T Pi Vi Pf Vf Pf Pi (6.24 104 Pa)( 2)
Vf
Pf 1 . 25 10 5 Pa
25
OXYGEN
12.5
300K
4
P(10 Pa)
150K
6.24
0 5 10
V ( m3 )
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EXAMPLE: Chapter 3
An ideal gas originally at temperature and pressure T1 , P1 is
compressed reversibly against a piston to a volume equal to
one-half its original volume. The temperature is varied during the
compression so that, at each instant, the relation P KV is satisfied.
(a) Draw an indicator diagram for the process.
(b) Find the work done in terms of n,R and the initial temperature.
isotherms
P P=KV
P1
V2 21 V1
T1
V2 V1
V
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1 2 2
V1 / 2 V1 / 2
(b) K
W PdV K VdV 4 V1 V1
V1 V1
2
3
W KV12
8
3
W nRT1
8
Work is done on the gas.
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EXAMPLE: Chapter 3
An ideal gas, and a block of Cu, have equal volumes of 0 . 500 m3
at 300K and 1 atmosphere. The pressure of each is increased
reversibly and isothermally to 5 atmospheres.
(a) Explain, with the aid of an indicator diagram, why the work is not
the same in the two processes.
(b) In which process is the work greater?
(c) Find the work done on each. For Cu, 0 . 7 10 6
atm1
.
(d) Find the change in volume for each case.
5 gas Cu
isotherms
P(atm) W=area under isotherm
Cu compressed much less
1
V0
0
V ( m3 ) 29
(b) Area under curve for gas > area under curve for Cu
W(on gas)>W(on Cu)
Vf
Pi 1
(c) Gas W PdV PiVi Pf V f V f Vi Vi
P 5
Vi f
Vi / 5
nRT PiVi dV
PiVi nRT P
V
V
W PiVi
Vi
V
1 N
1
W PiVi ln 1 . 01 10 5 2 0 . 5 m3 ln
5 m 5
0 W ( gas) 8 . 13 10 4 J
V V
Vf
Cu W PdV dV dT dP
Vi T P P T
Pf
1 V
dV VdP W VPdP
V P T Pi 30
, V constant
1
W V Pf2 Pi2
2
W
1 0 . 7 10 6
2 atm
0 . 5 m3 25 1 atm2 W (Cu) 0 . 424 J
1 1 4
(d) Ideal gas V f Vi V V f Vi Vi Vi Vi
5 5 5
V ( gas) 0 . 4 m3
V (Cu) 1 .4 10 6 m3
More elegantly,
Vf Vi V
Vf Pf
dV
Vi V Pi dP ln
Vi
P
ln
Vi
P
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But, for x<<1 ln(1 x) x
Vi V V V
Hence ln ln 1 P
Vi Vi Vi
V V i P as before
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EXAMPLE: Chapter 3
(a) Derive the general expression for the work per kilomole of a
van der Waals gas in expanding reversibly and at a constant T from
a specific volume v 1 to a specific volume v 2
(b) Find the work done when 2 kmoles of steam expand from a volume
of 30 m3 to a volume of 60 m3 at a temperature of 100 C
J m 3
m3
For steam a 580 10 3 b 0 . 0319
kmole2 kmole
(c) Find the work of an ideal gas in the same expansion.
a RT a
(a) P 2 ( v b) RT P 2
v vb v
v2 v
RT a a 2
W 2 dv RT ln( v b )
v1
vb v v v1
v2 b 1 1 v1 b 1 1
W RT ln
a
W RT ln
a
v1 b v 2 v1 v 2 b v1 v 2 33
(b) 2 kmoles of steam V1 30 m V2 60 m3 T 373 K
3
30m 3 m3
8.314 10 J
2kmole 2kmole
0.0319
3 J m
3 3
W 4 .267 10 J 6
V2 V2
nRT
(c) ideal gas W PdV dV
V1 V1
V V2
W nRT ln
V1
J
W 2 kmole 8 . 314 10 3
(373 K ) ln( 2 )
kmole K
W 4 .299 10 6 J
Not a great deal of difference. What is initial pressure?
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Now we have added new concepts and ideas:
Work has been introduced:
đW=PdV. It is not an exact differential
W is not a state function, but rather a process!
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